Selective C–O bond formation via a photocatalytic radical coupling strategy: access to perfluoroalkoxylated (ORF) arenes and heteroarenes

Abstract

Development of an efficient process that employs commercially available and cost effective reagents for the synthesis of perfluoroalkoxylated aromatic compounds (Ar–OR_F) remains a daunting challenge in organic synthesis. Herein, we report the first catalytic protocol using readily available perfluoroalkyl iodides (R_FI) and N-(hetero)aryl-N-hydroxylamides to access a wide range of perfluoroalkoxylated (hetero)arenes. Mild reaction conditions allow for selective O–R_F bond formation over a broad substrate scope and are tolerant of a wide variety of functional groups. Mechanistic studies suggest the formation and recombination of persistent N-hydroxyl radicals and transient R_F radicals under photocatalytic reaction conditions to generate N–OR_F compounds that rearrange to afford the desired products.